Pyrazolone monoazo dyestuffs



T e pr se t rivestiqii l f M iatented Nov. 17, 1 953 ATNENT oEFIcE MONQQZQ n s uFEs Werner Kuster; Basel, Switzerland, assignor, to J: R. 6;, Basel, Switzerland, a Swiss n p i g; Application December 3,1951

Claims priority, application. S witz eria nd T December .qqliesrned w a ns m? leme z d particularly "bath chrbmi g m th d and dye ng i' method-, also known e or ,me achrome method; is red' by the "wp'oi dyeing industry ews m emt n dyer toform a direct jud deyeloped on the goods and g. By no means all chrome t? .iiififip r is nee r a th chr e dyestufi: sufficient water to the fchromic acid salts in we, al o i ht t t al to weakly acid dyebath.

Y. i dyeh t. v a d fibre eyen in a neutr it has n w' tea found that on coupling hythe us u ethods ldiazotised 6 nitro-4 -a1-ky1 or -4- p9 'Y.-,,' chlrophenyl) -D sulphonic acid diamides, monoazodyestulffs' of gaear qr aia are obtained wherein R represents a .saturated hydrocarbon radical ,with from 4 to 8 carbon atoms and R and R represent hydrogen or a lower alkyl or lower hydroxyalkly radical, one X represents chlorine ,or hydrogenand the other X represents hydrogen. These monoazo dyestuffs .cause they allow; th v woo lco ponen in stapl fibres t be ia t--: yed whi e t s .1 91 rp tis protected-tothegeneatest n sm e xten The ,diazo componen ilsa c x ecord ngr to t i venfi-Qn-fi ld'iha li aisa ytaed ,zhr n anh 6 Claims. (01. 250-1631 radicalof from 4 tp-S carbon atoms 'inthe oi-posi- 'tion which can either have a straight: or branched chain or an" be alicylic, '6'-nitro?-4:-tert,-1amy1- 2-,a r n inophenol' is an advantageous "diazo; com- 5 onent. The-coupling components usable according to the i1 'yentipnf are obtained 'by condensati n ac cording'to the usualmethods fr'omBrihyr en'eor -a hydrazinochlorobenzened; amides andoxalacetic acidesters to produce 3' '-'s'ulphonic acid amidophenyD- o ch10 ophenyl) 5 pyraZOIOne Q-carbmiylicn acid sters are then converted intdt-lie corresponding 3-carboigyl-ic acidamides byf reacting them ammoniaor lower'primary aliphatic amines. The 3 -hyd razinobenzene-lesulphonic acid amides are produced from the corresponding amino compounds and may have a lower alkyl or lower hydroggyalkyl radical, for example a methyl, ethyl, hydroxyethyl' group, at the nitrogen atom of the sulphonamide group. A variation of the method to produce; the monoazo dyestuffs according to the invention, for which protection is also claimed, is that in many cases it is possible to couple the diazo components with 1-(3-sulphonic acid amidophenyl) or ch1orophenyD-5-pyrazo1one-3-carboxylic acid alkyl esters and then to it the amide fa let i r iar i e 0 t ee it er-this ie atie a f rexarnple 1 43- or orophen 1)-,

bath chroming process, the dyestuffs according to the present invention are superior to the similar known dyestufis having sulphonic acid or carboxyl groups as coupling components.

The following examples illustrate the invention without limiting it in any way. The temperatures are given in degrees centigrade and, where not otherwise stated, parts are given as. parts by weight. The relationship of parts by weight to parts by volume is that of kilograms to litres.

Example 1 22.4. parts of 6-nitro-2-amino-4-tert. amylphenol and 4.1 parts of sodium hydroxide are dissolved in 200 parts of water. 6.9 parts of sodium nitrite in 35 parts of water are added and the mixture is added dropwise to 25 parts by volume of cone. hydrochloric acid and 100 parts of water at a temperature not exceeding 3. In this way a suspension of the greenish-yellow diazo I body is obtained. On completion of the diazotisa- -tion the acidity of the diazo suspension is rendered neutral to Congo red with sodium bicarbonate whereupon a solution of 28.5 parts of 1- -phenylpyrazolone-3-carboxylic acid amide-3'- sulphonic acid amide (M. P. 220-222 on decomposition) and 8 parts of sodium hydroxide in 100 parts of water at -3 is added. The reaction mixture is made weakly phenol phthalein alkaline by the addition of 10 parts of 25% ammonia,

after which the temperature is slowly raised from f' is filtered off and dried. It is a dark violet powder which dissolves in water with a red-violet and in conc. sulphuric acid with,,a,brown-orange colour. The product, with advantage mixed with 10% of its weight of sodium carbonateand 2% of a dispersing agent, dyes wool from an acid bath in a brown-orange shade which on afterchroming changes to blue-red. A beautiful strong bluish-red shade is obtained by the single bath chroming process without, or with only a very slight addition of acid. The. bath is com- 1 pletely exhausted. The dyeings produced both by the after-chroming process as well as by the single bath chroming process have very good wet and light fastness properties.

Very similar dyestuffs which are also excellently suitable for the single bath chroming "process, are obtained if, in the above example,

the diazo component is replaced by 21.5 parts of .4-nitro-2-amino-4-tert. butylphenol or by 24 parts of 6-nitro-2-amino-4-cyclohexyl phenol or if the coupling component is replaced by 30 parts of 1-phenylpyrazolone-3-carboxylic acid methyl amide-3'-sulphonic acid amide or by 33 parts of 1-phenylpyrazolone-3-carboxylic acid ethanol I amide-3-sulphonic acid amide.

The pyrazolones mentioned above are obtained for example, by converting m-aminobenzene sulphonic acid amide (M. P. 142) by known methods phenol are diazotised as described in Example 1. -A solution of 31.5 parts of 1-phenylpyrazolone-3- '45 into the corresponding hydrazin an condensing the hydrazin with sodium oxalacetic acid ethyl ester to produce 1-phenylpyrazolone-3-carboxylic acid ethyl ester-8'-sulphonic acid amide. The 1-phen-y1pyrazolone-3-carboxylic acid ethyl ester-3'-sulphonic acid amide is then pasted with 5 times the amount of aqueous ammonia or 25% aqueous methylamine or 25% aqueous monoethanolamine and either left standing for 2 to 4 days at 20 or heated in a pressure vessel at- 80-100 for 10-15 hours. This causes the pyrazo-- lone carboxylic acid ethyl esters to dissolve, the alcohol radical of the ester being split ofi and replaced by the corresponding amide radical. 1-- phenylpyrazolone-3-carboxylic acid amide or methyl amide or monoethanol amide-3'-sulphonic acid amide is obtained according to the amine used.

Example 2 22.4 parts of 6-nitro-2-amino-4-tert. amylcarboxylic acid ethyl ester-3-sulphonic acid amide in 100 parts of water at 03 and 8 parts of sodium hydroxide are added to the diazo suspension after it has been neutralised with sodium bicarbonate. After about minutes the reaction mixture is made weakly phenolphthalein alkaline j after 20 hours.

. with ammonia andthe temperature is then slowly raised from 3 to 20. The coupling is completed The dyestufi which precipitates is filtered 01f and washed with a 2 /2% salt solution. The dyestufi in the form of a damp filter cake is pasted in 25% aqueous ammonia and left 3 to stand for 3-4 days. The paste is then diluted 1 with common salt solution and filtered; the residue is dried and'mixed with 10% of its weight of calcined soda and 2% of a dispersing agent.

The treatment with ammonia converts the 3- carboxylic acid ester group in the dyestufi also into the 3-carboxylic acid amide group which is recognisable by the considerably more bluish shade of the chromed dyeing on wool in comparison with an analogous dyeing obtained With-the starting material, 7

The dyestuff treated with ammonia described in this example is identical with the product fully described in Example 1.

Example 3 The coupling product of Example 2 is heated at room temperature in a closed vessel for 3 days with 20-30% aqueous methylamine. This changes the 3-carboxylic acid ethyl ester group into the B-carboxylic acid methylamide group and the product corresponds to the formula Similar conversions can be brought about in the same way with ethylamine or monoethanolamine. In each case dyestuffs are obtained which dye wool in strong bluish-red shades with good wet and light fastness properties and which are characterised by their particular suitability for use in the single bath-chroming process.

seam

Ekiiiimifale 4 a & so-moon di- 6.9 iifa1't5' oii 'sodiui'ir nitrite in 35 parts-6f water" addedto' aasolution of; 23:6 'partsioffi nitrdd amino i-cyclohexylphenol and 1 s -or "sodium? hydroxide in 200 parts of 'water: mixture. is'added'diopwise-"at 0==3 p i eenisli yellowsuspensionof:the diazo body is obtained. :Oncompletidn oi the dia'zotisation, the acidityof theldiazo 'su'spen'sion is :partly. neutralised with a little sodium bicarbonate and made neutral to Cbrigo iedwhereupon a solution of 31 parts of ,1- m

temperature slowly raised to "fzoriiurnfcoinpo u as-i aetesarter The dyestufff which precipitates and eams-es.

I is filtered "off, washed with 2l salt solution :dried, 'It is a ',darkjvi'olet' pdwder which aTred violtaniiiinconc. v rown-orange' shade. It

'advantageinixd ith %]0f its weightof sdai'emcartonate an %"or'a dispersing agent) an orange shade rrdm "anacid 1.15am and on after-chroming produces a strong bluish-red colour. The great advantage of this Lproductis that also in, a single bath chrom'ing ..p

steamer. (w

ocess and both without or with only a'very ghtj'addition of acid,v it dyes wool exactly the same'shade from a completely exhausted bath.

4 ycloheiiylphenol 'are'replaced by 22.4 parts of 6-nitro-2-aminoi-tert. famylphenol or 26.6 of16{nitro-2aniino=4-ootylphenol or if the arts "or 1 phnylpyrazolone-3-carboxylic acid yIaTrii de-S -sulphonic acid; methylamide are by 32.4 parts of l phenylpyrazolone-3- lie "acid methylamide-3-sulphonic "acid amide or 36.8 parts of l-phenylpyrazolone- H rbox'ylic acid methy1amide-3' -sulphonic acid noethanolamide. p Th y'razolon'es mentioned above are obtained starting from B aminobenZene sulphonemethylamide, -ethylamide or -monoethanolamide i. e. by condensationbf the corresponding hydrazine with sodium oxalacetic acid esters to o tain the corresponding lphenylpyrazolone-3- carbokyiic acid es'ter-3'-su1phonic acid alkylamides which by finally treating with aqueous .125% mthylainine are converted into the 3-carbo'x yl-ic acidmethylamides.

Example 5 21.0 "parts" of 6-nitro-l'2-amino 4-tert. butyl- "i5hi'id1 'and"4.1 parts of sodium hydroxide are dissolved in 200 parts of water and, together ery similar dyestufis'are obtained if, in the hours.

with a solution or 6.9" parts-or sodium nitrite in 35 parts of water are added dropwisdat il -3 to 25 parts by volume-oficonc. hydrochloric acid and 100 parts of water. The diazo compound forms a yellow colouredsuspension. On completion of the diazotisation, the acidity oflthe diazo suspension is made neutral to- Congo. red by the addition of a little sodium bicarbonate, after which a solutionof 32.0 parts of JI-(T- chlorophenyl) 5 pyrazolone .3 .carboxylic acid amide-5-sulphonicacid amide andfilparts of sodium hydroxide. in 100 parts of water is The reaction mixture. is. inside weakly phenolphthalein alkaline by the addition of about 10 parts of 25 aqueous-ammonia. The temperature is then-allowed to rise slowly .from

. 3 to 20 and the coupling is complete aiterj20 The dyestufi which precipitates .and

which corresponds to the formula bath chrommgproeesswiith no, oronly a" slight,

addition of acid. The bath iscompletelytiexhausted.

Very similar dyestufis are obtained 1 if,:' inthe above example,- the idiaz'o component-is replaced by 22.4 parts of 6 nitro z-amino i tert'. amylhexylphenolgor if thecouifling component is replaced by 33.5 p'arts of --'-1 (2"-chlorophenyl) 5- 'pyrazolone-3 carbokylic- 'acid 1 ester -5 -sul'pho'nic acid amide. The '1-' (-2-chlorophenyl-) -5-pyrazolone-3-carboxylic acid ethyl "est'er-5 s'ul'phonic acid amide is then pasted infi times the amount of 25% aqueous ammoniaor 25% aqueousmethylamine or 25% 'aqiieous'ethylamine and left standing at 20- fo1'-2-4 days orheatedin a pressure vessel to -100 for IO-15" hours. This causes the corresponding"pyrazolone :carboxylic acid ethyl'esters to dissolve, the alcohol radical of the ester beingsplit offand repl'aced'by the corresponding amide radical. .In this way 1-.'(2'- "acid amide-y methylami'deor "ethylamide 5'- "sulphonic acid amide obtained according to the amine use.

'Example 6 22.4 parts of 6-nitro-2-amino-4-tert. amylphenol and 4.1 parts of sodium hydroxide are dissolved in 200 parts of water, 6.9 parts of sodium nitrite in 35 parts of water are added and the mixture is added dropwise at a temperature not exceeding 3 to 35 parts by volume of cone. hydrochloric acid in 100 parts of water. A yellowish-green suspension of the diazo compound is obtained. On completion of the diazotisation, the acidity of the diazo suspension is neutralised with sodium bicarbonate until the reaction is neutral to Congo red whereupon a solution of 32.5 parts of 1-(4'-chlorophenyl) -5-pyrazolone- 3-carboxylic acid amide-5-su1phonic acid amide and 8 parts of sodium hydroxide in 100 parts of water is added at -3". The reaction mixture is made phenolphthalein alkaline with 10 parts of 25% ammonia and then the temperature is raised slowly from 3 to 20. The coupling is complete after 20 hours. The dyestufi which precipitates and which corresponds to the formula OzN - is filtered 01f, washed with 2 /g% salt water and dried.

It is a dark violet powder which dissolves in hot water with a bluish-red and in conc. sulphuric acid with an orange-brown colour. It is advantageous to grind the dyestufi well with some sodium carbonate and a dispersing agent. It dyes wool a yellowish-brown shade from an acid bath which changes on after-chroming to a bluish-red colour. Dyeings of the same shade and strength which have very good wet and light fastness properties are obtained according to the single bath chroming process with no, or only a slight, addition of acid. The bath is completely exhausted.

Very similar dyestuifs are obtained if, in the above example, the diazo component is replaced by 21.0 parts of 6-nitro-2-amino-4-tert. butylphenol or by 26 parts of 6-nitro-2-amino-4-octylphenol or if the coupling component is replaced by 34 parts of l(4'-chlorophenyl) -pyrazolone- 3-carboxylic acid amide-5'-sulphonic acid methylamide or by 35.5 parts of l-(4'-chloropheny1) 5-pyrazolone-3-carboxylic acid amide-5'-su1- phonic acid ethylamide.

The pyrazolones mentioned above are obtained by converting 4-chloraniline-5-sulphonic acid amide, -methylamide or -ethylamide by methods known per se into the corresponding hydrazins and condensing these hydrazins with sodium oxalacetic acid ethyl ester to the corresponding 1 (4' chlorophenyl) 5 pyrazolone 3 carboxylic acid ethyl ester-5'-sulphonic acid amide, -5 'sulphonic acid methylamide or -5'-sulphonic acid ethylamide. The pyrazolone-3-carboxylic 10-15 hours.

. coupling is complete after 20 hours.

acid ethyl esters so obtained are then pasted with 5 times the amount of 25% ammonia and then are either left standing at 20 for 2-4 days or heated in a pressure vessel to -100 for This causes the corresponding pyrazolone-S-carboxylic acid ethyl esters to dissolve, the alcohol radical of the ester being split off and replaced by the corresponding amide radical. In this way 1-(4'-chlorophenyl) -5- pyrazolone-B-carboxylic acid amide-5'-sulphonic acid amide, -5'-sulphonic acid methylamide or 5'-sulphonic acid ethylamide is obtained.

Example 7 22.4 parts of 6-nitro-2-amino-4-tert. amylphenol and 4.1 parts of sodium hydroxide are dissolved in 200 parts of water, 6.9 parts of sodium nitrite in 35 parts of water are added and the mixture is added dropwise at a temperature not exceeding 3 to 35 parts by volume of oonc. hydrochloric acid in parts of water. A greenish-yellow suspension of the diazo compound is obtained. On completion of the diazotisation, the acidity of the diazo suspension is neutralised with sodium bicarbonate until the reaction is neutral to Congo red whereupon a solution of 35.5 parts of l-(4-chlorophenyl)-5-pyrazolone- 3-carboxylic acid ethyl ester-5'-sulphonic acid amide and 8 parts of sodium hydroxide in 100 parts of water is added at 0-3". The reaction mixture is made phenolphthalein alkaline with 10 parts of 25% ammonia and then the temperature is raised slowly from 3 to 20. The

The dyestufi which precipitates is filtered off and washed with 2 salt water. The dyestuff, in the form of a damp filter cake, is pasted with 25% aqueous ammonia and left to stand for 3-4 days at room temperature. It is then diluted with common salt solution, filtered, dried and ground with sodium carbonate and a substance having a dispersing action. I

The treatment with ammonia converts the carboxylic acid ester group in the dyestufi also into the carboxylic acid amide group which is recognisable by the considerably more bluish shade of the chromed dyeing on wool in comparison with an analogous dyeing obtained wit the starting materials.

The dyestufi treated with ammonia described in this example is identical with the product fully described in Example 6.

Very similar dyeings are obtained if the coupling product of 6-nitro-2-amino-4-tert. amylphenol and 1- (4'-chlorophenyl) -5-pyrazolone-3- carboxylic acid ethyl ester-5'-sulphonic acid amide is treated with about 25% aqueous solutions of methyl-ethylor hydroxy-ethylamine instead of with ammonia. In this way, dyestuffs are obtained which have a carboxylic acid methylamide, ethylamide or hydroxyethylamide grou instead of the carboxylic acid ester group.

Example 8 0.2 part of the dyestuff obtained according to Example 1 is added to a solution of 1 part of dehydrated sodium sulphate, 02 part of sodium monochromate and 0.3 part of ammonium sulphate in 400 parts of water. 10 parts of wool are entered at 50, the bath is brought to the boil within 1 hour and kept at the boil for 1 hour to fully develop the shade. The wool, which has been dyed a bluish-red shade, is rinsed and dried.

9 What I claim is: 1. A monoazo dyestuff having the general formula:

SOf-NH-R" HIC- CH;

SOs-NH:

3. A monoazo dyestuff having the formula:

S O a-NH:

4. A monazo dyestuff having the formula:

5. A monoazo dyestufi having the formula:

-S O NH 6. A monoazo dyestufi having the formula:

( lz u SOP-NH:

WERNER; KUS'I'ER.

References Cited in the file of this patent UNITED STATES PATENTS Number Number Name Date Krebser et a1. Mar. 15, 1949 Kaiser Jan. 16, 1951 FOREIGN PATENTS Country Date Switzerland Apr. 16, 1927 Switzerland Oct. 16, 1944 

1. A MONOAZO DYESTUFF HAVING THE GENERAL FORMULA: 